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101.
A method is presented for the simultaneous determination of Cr(III) and Cr(VI) in yeast using species-specific double-spike
isotope dilution (SSDSID) with anion-exchange liquid chromatography (LC) separation and sector field inductively coupled plasma
mass spectrometric (SF-ICP-MS) detection. Total Cr is quantitated using ID SF-ICP-MS. Samples were digested on a hot plate
at 95±2 °C for 6 h in an alkaline solution of 0.5 M NaOH and 0.28 M Na2CO3 for the determination of Cr(III) and Cr(VI), whereas microwave-assisted decomposition with HNO3 and H2O2 was used for the determination of total Cr. Concentrations of 2,014±16, 1,952±103 and 76±48 mg kg−1 (one standard deviation, n=4, 3, 3), respectively were obtained for total Cr, Cr(III) and Cr(VI) in the yeast sample. Significant oxidation of Cr(III)
to Cr(VI) (24.2±7.6% Cr(III) oxidized, n=3) and reduction of Cr(VI) to Cr(III) (37.6±6.5% Cr(VI) reduced, n=3 ) occurred during alkaline extraction and subsequent chromatographic separation at pH 7. Despite this significant bidirectional
redox transformation, quantitative recoveries for both Cr(III) and Cr(VI) were achieved using the SSDSID method. In addition,
mass balance between total Cr and the sum of Cr(III) and Cr(VI) concentrations was achieved. Method detection limits of 0.3,
2 and 30 mg kg−1 were obtained for total Cr, Cr(VI) and Cr(III), respectively, based on a 0.2-g sub-sample. 相似文献
102.
建立了大米、小麦和大豆中黄曲霉毒素B1、黄曲霉毒素B2、黄曲霉毒素G1、黄曲霉毒素G2、伏马毒素B1、伏马毒素B2、柄曲霉素和异烟棒曲霉素C 8种真菌毒素的高效液相色谱-串联质谱(HPLC-MS/MS)分析方法。样品加入正己烷去除油脂,用60%乙腈振荡液液分配提取,取乙腈水层过滤膜后分析。在电喷雾电离(ESI)正离子模式下采用多反应监测(MRM)进行测定。定量方法采用同位素内标稀释法,8种真菌毒素在各自浓度范围内线性关系良好,线性系数均不低于0.997 0。空白样品的加标回收率为77%~123%,相对标准偏差(RSD)为0.6%~13.3%。该方法操作简单、灵敏度高,可用于粮谷中真菌毒素的检测。 相似文献
103.
液相色谱/串联质谱线性组合法测定动物组织中硝基呋喃代谢产物 总被引:19,自引:0,他引:19
研究了对动物组织中4种硝基呋喃类代谢产物AMOZ、AHD、SEM、AOZ的同位素稀释HPLC—MS/MS线性组合分析方法,以2-基苯甲醛作为衍生化试剂,AMOZ—d5、AOZ-4作内标,用乙酸乙脂提取,用自制的净化试剂净化,以乙腈-0.1%甲酸为流动相,采用梯度洗脱,可适应不同种类的动物组织样品前处理,15min可将4种代谢产物完全分离并测定。提出了HPLC—MS/MS多重反应监测线性组合法的原理并进行了验证,回收率为85%-118%;定量限(LOQ)为0.1μg/kg;检出限(LOD)为0.03μg/kg。 相似文献
104.
Fragmentation pathways of a series of pentacoordinated bisaminoacylspirophosphoranes were elucidated by electrospray ionization multistage mass spectrometry (ESI-MS(n)) in negative mode. The deprotonated ions of pentacoordinated bisaminoacylspirophosphoranes tend to eliminate a corresponding amino acid to form base peak. The hydrogen/deuterium exchange experiment, the high-resolution mass spectrometry, (13)C stable isotope labeling experiment and theoretical calculations were used to rationalize the proposed fragmentation pathways and to verify the differences between the fragmentation pathways. The results indicate that the negative molecular ions of pentacoordinated bisaminoacylspirophosphoranes dissociate through its open-chain tricoordinated tautomers. The relative Gibbs free energies (ΔG) of the product ions and proposed fragmentation pathways were estimated using the B3LYP/6-31 + + G(d, p) model. The results have some potential applications in the identification structures of similar spirophosphorane compounds by ESI-MS(n). 相似文献
105.
Tomislav P. ivkovi 《Journal of mathematical chemistry》2009,45(4):1060-1101
Mathematical formalism of the Low Rank Perturbation method (LRP) is applied to the vibrational isotope effect in the harmonic
approximation with a standard assumption that force field does not change under isotopic substitutions. A pair of two n-atom isotopic molecules A and B which are identical except for isotopic substitutions at ρ atomic sites is considered. In the LRP approach vibrational frequencies ω
k
and normal modes of the isotopomer B are expressed in terms of the vibrational frequencies ν
i
and normal modes of the parent molecule A. In those relations complete specification of the normal modes is not required. Only amplitudes at sites τ affected by the isotopic substitutions and in the coordinate direction s (s = x, y, z) are needed. Out-of-plane vibrations of the (H,D)-benzene isotopomers are considered. Standard error of the LRP frequencies
with respect to the DFT frequencies is on average . This error is due to the uncertainty of the input data (± 0.5 cm−1) and in the absence of those uncertainties and in the harmonic approximation it should disappear. In comparing with experiment,
one finds that LRP frequencies reproduces experimental frequencies of (H,D)-benzene isotopomers better () than scaled DFT frequencies () which are designed to minimize (by frequency scaling technique) this error. In addition, LRP is conceptually and numerically
simple and it also provides a new insight in the vibrational isotope effect in the harmonic approximation. 相似文献
106.
Rate Coefficients and Kinetic Isotope Effects of Cl+XCl→XCl+Cl (X=H,D, Mu) Reactions from Ring Polymer Molecular Dynamics 下载免费PDF全文
The ring-polymer molecular dynamics (RPMD) was used to calculate the thermal rate coefficients and kinetic isotope effects of the heavy-light-heavy abstract reaction Cl+XCl\begin{document}$ \rightarrow $\end{document} XCl+Cl (X = H, D, Mu). For the Cl+HCl reaction, the excellent agreement between the RPMD and experimental values provides a strong proof for the accuracy of the RPMD theory. And the RPMD results are also consistent with results from other theoretical methods including improved-canonical-variational-theory and quantum dynamics. The most novel finding is that there is a double peak in Cl+MuCl reaction near the transition state, leaving a free energy well. It comes from the mode softening of the reaction system at the peak of the potential energy surface. Such an explicit free energy well suggests strongly there is an observable resonance. And for the Cl+DCl reaction, the RPMD rate coefficient again gives very accurate results compared with experimental values. The only exception is at the temperature of 312.5 K, results from RPMD and all other theoretical methods are close to each other but slightly lower than the experimental value, which indicates experimental or potential energy surface deficiency. 相似文献
107.
半导体同位素电池由于其寿命长、集成性优良、环境适应性强等特点成为解决MEMS能源问题的理想手段。利用4H-SiC材料的宽禁带特性,制造了4H-SiC肖特基同位素电池。对电池的耗尽层厚度以及掺杂浓度进行了优化设计,对肖特基金属进行了选择。使用4mCi/cm2的63Ni作为同位素电池的放射源对制造的同位素电池进行了测试。测试结果表明,该同位素电池可以获得31.3nW/cm2的功率密度、0.5V的开路电压、3.13×10-8A/cm2的短路电流密度和1.3%的转换效率。将电池的输出特性和硅基的平板型、3D结构电池输出特性进行了比较,证明4H-SiC肖特基同位素电池能够获得较高的功率密度。电池的性能可通过提升势垒高度、提高工艺质量、更换同位素等方式得到提高。 相似文献
108.
Theoretical calculation of the partial cross section for first vibrational excitation in He-H2(D2,T2) collisions 下载免费PDF全文
In this paper, close-coupling method was applied to the He-H2 (D2,T2) system, and the first vibrational excitation cross sections of '00-10, 00-12, 00-14, 00-16' at different incident energy have been calculated. By analyzing the ditferences of these partial wave cross sections, this paper have obtained the change rules of the partial wave cross sections with increases of quantum number, and with change of reduced mass of system. Based on the calculation, influence on the partial wave cross sections brought by the variations in the reduced mass of systems and in the relative kinetic energy of incident atoms is discussed.[第一段] 相似文献
109.
报道了600MeV(18)O轰击(nat)Ph(厚靶)生成的质量数在180—209之间的Hg同位素产物独立截面的测量结果.通过与600MeV质子轰击天然铅靶生成Hg同位素产额分布的比较,讨论了几个质量区段Hg同位素的生成机制.测量结果也与相对论重离子碎裂反应双质子移出道的产额分布进行了比较.结果表明,中能重离子与中子较富集靶核组成的反应系统对生成丰中子类靶余核具有较明显的优势. 相似文献
110.
The most neutron-deficient isotopes 215;216U were produced in the complete-fusion reaction 180W(40Ar, 4-5n)215,216U. Evaporation residues recoiled from the target were separated in-flight from the primary beam by the gas-filled recoil separator SHANS and subsequently identified on the basis of correlated -decay chains. Two -decaying states were identified in 216U, one for the ground state and the other for the isomeric state with 8+(h9=2f7=2) configuration. The -decay properties for 215;216U and the systematics of 8+ isomeric state in N =124,126 isotones were investigated. 相似文献